WO2022163543A1 - 樹脂成形体の再利用方法 - Google Patents
樹脂成形体の再利用方法 Download PDFInfo
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- WO2022163543A1 WO2022163543A1 PCT/JP2022/002283 JP2022002283W WO2022163543A1 WO 2022163543 A1 WO2022163543 A1 WO 2022163543A1 JP 2022002283 W JP2022002283 W JP 2022002283W WO 2022163543 A1 WO2022163543 A1 WO 2022163543A1
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- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0217—Mechanical separating techniques; devices therefor
- B29B2017/0224—Screens, sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0255—Specific separating techniques using different melting or softening temperatures of the materials to be separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0293—Dissolving the materials in gases or liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B2017/0424—Specific disintegrating techniques; devices therefor
- B29B2017/0468—Crushing, i.e. disintegrating into small particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B2017/0424—Specific disintegrating techniques; devices therefor
- B29B2017/0484—Grinding tools, roller mills or disc mills
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/38—Polymers of cycloalkenes, e.g. norbornene or cyclopentene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the present invention relates to a method for reusing resin moldings.
- Thermoplastic resins such as polymers having an alicyclic structure generally have excellent properties such as transparency, heat resistance, moisture resistance, chemical resistance, and electrical properties, and are therefore used as optical materials, medical materials, and electrical component materials. It is widely used in various fields such as For this reason, a large amount of waste materials of molded articles containing the alicyclic structure-containing polymer and processing waste materials generated during the production of the molded articles are generated.
- a thermoplastic resin is usually formed into a film by solution drooling or melt extrusion, stretched as necessary, and wound into a roll to form a long and wide film. Supplied as a rotating body. During this process, the edges of the film are trimmed, resulting in what is generally called the edge of the film as waste material.
- recycled plastics which are obtained by collecting waste materials of moldings made of thermoplastic resin, pulverizing them as necessary, and pelletizing them, are widely used.
- the waste material of a molded product made of a polymer resin having an alicyclic structure is reused, physical properties such as strength and color tone may decrease due to residual foreign matter and thermal deterioration due to repeated thermal processing, and the intended use of the product may decrease. could not be used for
- Patent Document 1 discloses a process of removing foreign matter in a molten state or a solution state of an alicyclic structure-containing polymer resin molded article.
- a method for recycling an alicyclic structure-containing polymer resin molding comprising: Further, in Patent Document 2, an alicyclic structure-containing polymer resin molded article is disclosed, which includes a step of dissolving the alicyclic structure-containing polymer resin molded article in a solvent and decolorizing it with an adsorbent. A recycling method is disclosed. Further, Patent Literature 3 discloses a method for recycling an alicyclic structure-containing polymer resin molding, which includes a step of hydrogenation treatment.
- the present invention provides a method for reusing a resin molded article containing an alicyclic structure-containing polymer, which can suppress appearance defects and obtain a recycled resin molded article having improved physical properties such as color tone. intended to provide
- the inventors conducted intensive studies with the aim of solving the above problems. Then, the present inventor pulverized a resin molding containing an alicyclic structure-containing polymer, and mixed cyclohexane and a hydrocarbon-based or aromatic-based solvent having a freezing point below a predetermined temperature in a predetermined ratio. The present inventors have found that by dissolving in a solvent, it is possible to obtain a recycled product of a resin molded product with improved physical properties such as color tone while suppressing defects in appearance, thereby completing the present invention.
- an object of the present invention is to advantageously solve the above problems, and a method for recycling a resin molded article of the present invention comprises pulverizing a resin molded article containing an alicyclic structure-containing polymer.
- the pulverized molded body is sieved with a sieve of ⁇ 3 mm or more and 15 mm or less.
- it further comprises the step of: By sieving the molded body with a sieve having a diameter equal to or less than the above upper limit to reduce the size of the pulverized molded body to be melted, the dissolution time is further shortened, the dissolution efficiency is improved, and the recycled product is produced. It can contribute to suppressing defects in appearance to improve physical properties such as color tone and shortening the process time.
- the diameter of the sieve to be equal to or greater than the above lower limit, it is possible to suppress a decrease in recovery efficiency due to pulverized compacts that do not pass through the sieve.
- the boiling point of the solvent is preferably 150°C or less.
- the boiling point of the mixed solvent can be lowered.
- the drying time for removing the mixed solvent from the polymer solution by drying and recovering the resin is shortened, the deterioration of the resin due to high temperature drying is suppressed, and the solvent remaining in the resin is suppressed.
- the method for reusing a resin molded body of the present invention further includes a step of adding an adsorbent to the system for dissolving the pulverized molded body.
- an adsorbent By adding an adsorbent, it is possible to adsorb and remove foreign substances (e.g., soluble foreign substances such as degraded substances of antioxidants) in the polymer solution. can contribute to improving the physical properties of
- the adsorbent is preferably acid clay, activated clay, activated alumina, or zeolite. These adsorbents can satisfactorily adsorb soluble contaminants such as degraded substances of antioxidants.
- the method for reusing a resin molding of the present invention further includes a step of filtering the polymer solution in a solution state to remove foreign substances and adsorbents.
- Filtration in a solution state removes insoluble contaminants (e.g., additional materials other than alicyclic structure-containing polymers such as urethane), adsorbents, and soluble contaminants adsorbed to the adsorbent (e.g., oxidation Degraded substances of the inhibitor) can be removed, and appearance defects of the recycled product can be suppressed to a lesser extent, and physical properties such as color tone can be improved.
- the ratio of the amount of the pulverized molded article to the total amount of the mixed solvent and the pulverized molded article in the polymer solution when the solution is filtered is 10% by weight. % or more and 20% by weight or less.
- the ratio of the amount of the molded product to the total amount of the mixed solvent and the molded product (filtration concentration) is equal to or higher than the above lower limit, the excessive amount of the solvent causes die buildup due to the residual solvent during pelletization (melt extrusion). It is possible to suppress the generation of such particles, thereby contributing to a decrease in resin recovery efficiency and suppression of deterioration of the apparatus.
- the filtration concentration is equal to or less than the above upper limit, it is possible to prolong the dissolution time and the solution filtration time, and to eliminate the generation of foreign matter due to the increase in the differential pressure of the solution filtration, and to reduce the appearance defects of the recycled product. It can be suppressed to improve physical properties such as color tone and contribute to shortening of the process time.
- the method for reusing the resin molded product of the present invention comprises the steps of removing the mixed solvent from the polymer solution to recover the resin containing the alicyclic structure-containing polymer, melting the recovered resin, It is preferable to further include a step of filtering the resin in a molten state. Filtration in a molten state (melt filtration) can remove non-melting foreign matter (e.g. resin degradation components such as scorch components), and can reduce appearance defects of recycled products and improve physical properties such as color tone. can contribute to
- the glass transition temperature of the alicyclic structure-containing polymer is preferably 70°C or higher and 170°C or lower.
- Tg glass transition temperature
- the alicyclic structure-containing polymer is a norbornene polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, or a vinyl alicyclic hydrocarbon.
- the alicyclic structure-containing polymer selected from the group consisting of polymers and hydrogenated products thereof may be an amorphous resin.
- the method of the present invention can be suitably applied to these polymer resins in order to reduce appearance defects of recycled products and improve physical properties such as color tone.
- the resin molded body as a raw material may have a urethane layer with a thickness of 100 nm or less.
- the urethane layer can be removed to a high degree as a foreign substance. It can be preferably applied to improve physical properties such as color tone by suppressing it to a lesser extent.
- the method for reusing the resin molded article of the present invention includes a step of pulverizing a resin molded article containing an alicyclic structure-containing polymer to obtain a pulverized molded article (“pulverization step"), and the pulverized compact is mixed with 80% by weight or more and 98% by weight or less of cyclohexane and 2% by weight or more and 20% by weight or less of a hydrocarbon system with a freezing point of -40 ° C or less or It is characterized by including a step of dissolving in a mixed solvent containing an aromatic solvent to obtain a polymer solution (“dissolving step”).
- the method of the invention may further comprise any one or more of the following steps: - A step of sieving the pulverized molded product between the step of pulverizing the resin molded product and the step of dissolving the pulverized molded product (sieving step); - A step of adding an adsorbent to the pulverized product dissolution system (adsorbent addition step); - A step of filtering the polymer solution in a solution state to remove foreign matter and adsorbent (solution filtering step); - The step of adding an antioxidant to the filtered polymer solution (antioxidant addition step); - The step of removing the mixed solvent from the polymer solution to recover the resin containing the alicyclic structure-containing polymer (solvent removal step); - A step of melting the resin recovered in the solvent removal step (melting step); - A step of filtering the molten resin in a molten state (melt filtration step); A step of pelletizing a molten resin to obtain a pelletized resin as a recycled product
- the alicyclic structure-containing polymer which is a component of the resin molding as a raw material and a recycled product, has an alicyclic structure in its main chain and/or side chain, and has mechanical strength and heat resistance. From the viewpoint of properties and the like, those containing an alicyclic structure in the main chain are preferred.
- Alicyclic structures include saturated alicyclic hydrocarbon (cycloalkane) structures and unsaturated alicyclic hydrocarbon (cycloalkene) structures.
- An alkene structure is preferred, and a cycloalkane structure is most preferred.
- the number of carbon atoms constituting the alicyclic structure is not particularly limited, but when it is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, mechanical strength, Properties such as heat resistance are highly balanced and suitable.
- the proportion of repeating units containing an alicyclic structure in the polymer resin having an alicyclic structure used in the present invention may be appropriately selected depending on the purpose of use. More preferably 50% by weight or more, particularly preferably 70% by weight or more, and most preferably 90% by weight or more. It is preferable from the viewpoint of the transparency and heat resistance of the resin molding that the proportion of the repeating unit having an alicyclic structure in the polymer having an alicyclic structure is within this range.
- the polymer resin having an alicyclic structure includes (1) norbornene-based polymer, (2) monocyclic cyclic olefin-based polymer, (3) cyclic conjugated diene-based polymer, (4) vinyl Examples include alicyclic hydrocarbon polymers and hydrogenated products thereof. Among these, norbornene-based polymers are more preferable from the viewpoint of transparency and moldability.
- norbornene-based polymers include ring-opening polymers of norbornene-based monomers, ring-opening copolymers of norbornene-based monomers and other ring-opening copolymerizable monomers, and hydrogenated products thereof
- norbornene-based Examples include addition copolymers of monomers, addition copolymers of norbornene-based monomers and other copolymerizable monomers, and the like.
- hydrogenated ring-opening (co)polymers of norbornene-based monomers are most preferable from the viewpoint of transparency.
- the above polymer having an alicyclic structure is selected from known polymers disclosed in, for example, JP-A-2002-321302.
- the glass transition temperature (Tg) of the alicyclic structure-containing polymer may be appropriately selected according to the purpose of reuse. It may be preferably, for example, 70° C. or higher, preferably 100° C. or higher, more preferably 120° C. or higher. Tg can be measured, for example, by the method described in the Examples of this specification.
- the melt index (MI) of the alicyclic structure-containing polymer resin molding may be, for example, within ⁇ 20% of the center, preferably within ⁇ 15% of the center, and more preferably within ⁇ 10% of the center. When the MI is within this range, stable extruded products and injection molded products can be obtained, which is preferable. MI can be measured, for example, under conditions of 250 to 280° C. and a load of 2.16 kgf.
- Molded bodies to be reused include molded bodies for optical purposes such as lenses, prisms, optical films, optical sheets, optical disk substrates, light guide plates, light guides, optical fibers, and mirrors; disposable syringes, chemical vials, film for packaging chemicals, Medical moldings such as inspection cells, inspection containers, infusion bags, syringe rods; electrical or electronic materials such as wire coatings, wafer shippers, capacitor films, circuit boards, connectors and other sheets, films, plates, containers, insulating materials, etc. Molded products for use: plates, pipes, round bars, bottles, building materials, stationery, and the like.
- the molded article to be reused may be, for example, a waste material of the molded article, a processing waste material generated during the production of the molded article (eg, film lugs, leftovers from die cutting), or a used molded article.
- a molded body to be reused may be a molded body derived from a synthesized resin (virgin material) or a molded body derived from a recycled resin (recycled product).
- the thickness of the molded body may be, for example, 30 ⁇ m or more, preferably 40 ⁇ m or more, more preferably 50 ⁇ m or more, and for example, 100 ⁇ m or less, preferably It may be 90 ⁇ m or less, more preferably 80 ⁇ m or less.
- the resin molding as a raw material may have a part formed of an additional material other than the alicyclic structure-containing polymer, in addition to the part formed of the alicyclic structure-containing polymer.
- additional materials may be in the form of layers (coatings, laminates).
- additional materials may be organic or inorganic.
- additional materials include, for example, adhesive substances (eg, polyurethane, acrylic resin, polyester), coloring substances.
- adhesive substances eg, polyurethane, acrylic resin, polyester
- coloring substances eg, polyurethane, acrylic resin, polyester
- Such additional materials may be layered and the layer thickness may be for example 10 nm or more, preferably 20 nm or more, more preferably 30 nm or more, for example 100 nm or less, preferably 90 nm or less, More preferably, it may be 80 nm or less.
- the method of the present invention can remove such additional materials as foreign matter to a high degree, particularly when a solution filtration step is performed, according to the method of the present invention. Even when a polymer resin having a portion formed of a material is used as a raw material, it can be suitably applied to improve physical properties such as color tone by suppressing appearance defects of recycled products.
- the method of the present invention includes a step of pulverizing a resin molded product as a raw material to obtain a pulverized molded product.
- the pulverization of the resin molding can be performed using, for example, a pulverizer or a cutter.
- the method of the present invention may further include a step of sieving the pulverized molded product with a sieve having a predetermined hole diameter ( ⁇ ) between the step of pulverizing the resin molded product and the step of dissolving the pulverized molded product.
- the predetermined hole diameter may be, for example, 3 mm or more, preferably 4 mm or more, more preferably 5 mm or more, and may be, for example, 15 mm or less, preferably 12 mm or less, more preferably 10 mm or less.
- the dissolution time is further shortened, the dissolution efficiency is improved, and the recycled product is produced. It can contribute to suppressing defects in appearance to improve physical properties such as color tone and shortening the process time.
- the diameter of the sieve is equal to or greater than the above lower limit, it is possible to suppress a decrease in recovery efficiency due to pulverized compacts that do not pass through the sieve.
- the method of the present invention includes a step of dissolving the pulverized compact in a solvent.
- insoluble foreign matter e.g., resin deterioration components such as burnt components, coatings such as urethane
- solubility It is possible to facilitate removal (eg, removal by adsorption) of foreign substances (eg, degraded substances of antioxidants).
- the solvent is a mixed solvent containing 80% by weight or more and 98% by weight or less of cyclohexane and 2% by weight or more and 20% by weight or less of a hydrocarbon or aromatic solvent having a freezing point of ⁇ 40° C. or less with respect to 100% by weight of the mixed solvent. is.
- the freezing point of the solvent is -40°C or lower.
- the freezing point of a solvent can be measured, for example, by reading the crystallization temperature with a differential scanning calorimeter.
- the solvent having the above freezing point may be appropriately selected from solvent compounds whose physical properties are disclosed.
- the solvent is not particularly limited as long as it achieves the object of the present invention, but for example, n-hexane (freezing point -95°C, boiling point 69°C), n-heptane (freezing point -91°C, boiling point 98.4°C), Hydrocarbon solvents such as methylcyclohexane (freezing point -126 ° C, boiling point 100 ° C), and toluene (freezing point -93 ° C, boiling point 111 ° C), xylene (freezing point -50 ° C, boiling point 140 ° C), trimethylbenzene (freezing point - 44.8° C., boiling point 164.7° C.).
- the solvent may be one kind or a mixture of two or more kinds.
- the solvent preferably has a boiling point (boiling point under atmospheric pressure of about 101.3 kPa) of 150°C or lower, more preferably 150°C or lower, and particularly preferably 140°C or lower.
- the boiling point of the solvent can be measured, for example, at the equilibrium reflux boiling point.
- the solvent having the above boiling point may be appropriately selected from solvent compounds whose physical properties are disclosed.
- solvents are not particularly limited as long as the object of the present invention is achieved, but examples include hydrocarbon solvents such as n-hexane, n-heptane and methylcyclohexane, and aromatic solvents such as toluene and xylene. Solvents may be mentioned.
- a solvent compound that is compatible with cyclohexane and is a good solvent for the alicyclic structure-containing polymer is usually used. All of the solvent examples given above correspond to such solvent compounds.
- the content of the solvent in the mixed solvent may be 2% by weight or more, preferably 3% by weight or more, and more preferably 5% by weight or more with respect to 100% by weight of the mixed solvent. If the solvent content is too low, the solvent or polymer solution tends to solidify in a cold environment such as winter, which can cause problems in operation. In addition, it becomes difficult to pre-coat the filter body in the container containing the polymer solution (fix the filter body to the discharge hole on the bottom of the container by sedimentation), and the polymer solution may flow out without removing foreign substances by filtration. In order to prevent these problems, the solvent content is preferably at least the above lower limit.
- the content of the solvent in the mixed solvent may be 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less with respect to 100% by weight of the mixed solvent. If the content of the solvent is too high, the resin component tends to precipitate from the polymer solution, which may reduce the recovery efficiency of the recycled resin product or cause troubles in operation. In order to prevent these problems, the content of the solvent is preferably not more than the above upper limit.
- the content of cyclohexane in the mixed solvent may be the total amount remaining after removing the solvent from the mixed solvent.
- the content of cyclohexane in the mixed solvent may be 80% by weight or more, preferably 85% by weight or more, and more preferably 90% by weight or more with respect to 100% by weight of the mixed solvent.
- the content of cyclohexane in the mixed solvent may be 98% by weight or less, preferably 97% by weight or less, and more preferably 95% by weight or less with respect to 100% by weight of the mixed solvent.
- the amount of the pulverized molded product to be added is not particularly limited as long as the method of the present invention can be carried out. For example, it may be 10% by weight or more, preferably 11% by weight or more, more preferably 12% by weight or more, and may be, for example, 20% by weight or less, preferably 19% by weight or less, more preferably 18% by weight or less. good. If the amount added to the molded product is too small, the amount of solvent will be excessive, and the solvent will remain even after removing the solvent. The resin adheres to the core and deteriorates thermally, causing foreign matter and making the strand unstable.
- the addition amount of the molded body is not less than the above lower limit. If the amount of the molded article added is too large, the dissolution time and the solution filtration time will be prolonged, and foreign matter may be generated due to an increase in differential pressure during solution filtration. In order to prevent these problems, it is preferable that the amount of the molded body added is equal to or less than the above upper limit.
- the temperature at which the molded body is dissolved in the solvent is not particularly limited as long as the molded body can be dissolved.
- the temperature may be 80° C. or lower, preferably 75° C. or lower, more preferably 70° C. or lower.
- the method of the present invention preferably further includes the step of adding an adsorbent to the system for dissolving the pulverized compact.
- the term "adding an adsorbent to the system for dissolving the pulverized product of the molded body” means that the adsorbent may be added so as to be in contact with the polymer solution, for example, it may be added to the polymer solution, and the molded body It may be added to the mixed solvent used for dissolving the pulverized product, may be added to the mixed solvent together with the pulverized product, or may be added in advance to the container used for dissolution.
- adsorbent By adding an adsorbent, it is possible to adsorb and remove foreign substances (e.g., soluble foreign substances such as degraded substances of antioxidants) in the polymer solution. can contribute to improving the physical properties of Such adsorbents include, for example, acid clay, activated clay, activated alumina, and zeolites. These adsorbents can satisfactorily adsorb soluble contaminants such as degraded substances of antioxidants.
- the amount of adsorbent may be, for example, 2.0 parts by weight or more, preferably 2.5 parts by weight or more, and more preferably 3.0 parts by weight or more with respect to 100 parts by weight of the mixed solvent. It may be 0 parts by weight or less, preferably 4.5 parts by weight or less, more preferably 4.0 parts by weight or less.
- the method of the present invention preferably further includes a step of filtering the polymer solution in a solution state to remove foreign substances and adsorbents.
- filtration in a solution state removes insoluble foreign matter (e.g., additional materials other than the alicyclic structure-containing polymer, such as urethane), adsorbent, and soluble foreign matter adsorbed to the adsorbent.
- insoluble foreign matter e.g., additional materials other than the alicyclic structure-containing polymer, such as urethane
- adsorbent e.g., urethane
- soluble foreign matter adsorbed to the adsorbent e.g., degraded substances of antioxidants
- Solution filtration may be performed using a filter aid as a filter bed.
- filter aids include diatomaceous earth (eg, trade name “Radiolite”) and perlite (eg, trade name “Topco”).
- the ratio of the amount of the compact in the solution to the total amount of the mixed solvent and the compact in the solution at the time of solution filtration may not be adjusted as it is when the compact is dissolved, and the dilution with the mixed solvent may be adjusted, for example, 10% by weight or more, preferably 11% by weight or more, more preferably 12% by weight or more, for example 20% by weight or less, preferably 19% by weight or less, More preferably, it may be 18% by weight or less. If the filtration concentration is too low, the amount of solvent will be excessive, and the solvent will remain even after removing the solvent, and the residual solvent will cause die buildup during pelletization (melt extrusion), and the resin will remain at the outlet of melt extrusion.
- the filtration concentration is preferably equal to or higher than the above lower limit. If the filtration concentration is too high, the dissolution time and solution filtration time will be prolonged, and contaminants may be generated due to the increased differential pressure of solution filtration. In order to prevent these problems, the filtration concentration is preferably equal to or less than the above upper limit.
- Solution filtration may be performed, for example, by pressure filtration or vacuum filtration.
- pressure filtration the differential pressure between the inlet and outlet of the filter may be, for example, 0.2 MPa or more, preferably 0.24 MPa or more, and may be, for example, 1.0 MPa or less, preferably 0.8 MPa or less.
- the differential pressure between the inlet and outlet of the filter may be, for example, 0.2 MPa or more, preferably 0.4 MPa or more.
- the differential pressure refers to the differential pressure at the highest differential pressure during filtration. If the differential pressure of solution filtration is equal to or higher than the above lower limit, it is possible to improve the solution filtration rate while improving the foreign matter removal rate in the solution.
- the temperature at which solution filtration is performed is not particularly limited as long as the polymer solution can be filtered. , preferably 75° C. or lower, more preferably 70° C. or lower.
- the method of the present invention further comprises adding an antioxidant to the filtered polymer solution.
- an antioxidant is blended in a resin molded article to be reused, and at least a part of the antioxidant may be degraded during use of the resin molded article. Therefore, this step can replenish the antioxidant that has disappeared due to deterioration.
- general antioxidants for alicyclic structure-containing polymer resins can be used, and examples thereof include phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. However, among these, phenolic antioxidants are preferred, and alkyl-substituted phenolic antioxidants are particularly preferred.
- phenolic antioxidant for example, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4 -Methylphenyl acrylate, 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate, etc.
- phosphite tris(dinonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9, monophosphite compounds such as 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecylphosph phyto), 4,4′ isopropylidene-bis(phenyl-di-alkyl (C12-C15) phosphite) and other diphosphite compounds.
- monophosphite compounds are preferred, and tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite and the like are particularly preferably used. ing.
- sulfur-based antioxidants examples include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate, pionate, pentaerythritol-tetrakis-( ⁇ -lauryl-thio-propionate, 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, etc. be done.
- antioxidants may be used alone or in combination of two or more.
- the amount of the antioxidant compounded is not particularly limited as long as it does not impair the characteristics of the recycled product.
- it may be 0.2 parts by weight or more, preferably 0.3 parts by weight or more, more preferably 0.4 parts by weight or more, for example 1.0 parts by weight or less, preferably 0.8 parts by weight or less, or more
- it may be 0.7 parts by weight or less.
- the method of the present invention preferably further includes the step of removing the mixed solvent from the polymer solution to recover the resin containing the alicyclic structure-containing polymer.
- the mixed solvent can be removed, for example, by drying the mixed solvent. Drying of the mixed solvent may be carried out, for example, by heat drying, drying under reduced pressure, or drying under heat under reduced pressure.
- the temperature for drying by heating or drying under reduced pressure by heating is not particularly limited as long as the mixed solvent can be removed. It may be 320° C. or lower, preferably 310° C. or lower, more preferably 300° C. or lower.
- the pressure for drying under reduced pressure or drying under reduced pressure by heating is lower than atmospheric pressure, and may be, for example, ⁇ 90 kPa or less, preferably ⁇ 95 kPa or less, more preferably ⁇ 100 kPa or less.
- the resin may be recovered in a molten state.
- the recovered resin may be directly used as a recycled resin for molding a recycled resin molded product, but it is preferable to continue to subject the collected resin to a melting process or a melt filtration process.
- the method of the present invention preferably further includes a step of melting the resin containing the alicyclic structure-containing polymer recovered in the solvent removal step. Melting can be performed by heating the recovered resin.
- the melting temperature can be appropriately determined depending on the type of the alicyclic structure-containing polymer, and may be, for example, 250°C or higher, preferably 260°C or higher, more preferably 270°C or higher, for example, 320°C. Below, preferably 310° C. or lower, more preferably 300° C. or lower.
- the solvent removing step also serves as the melting step.
- the molten resin obtained in the melting step may be used as a recycled resin as it is for molding a recycled resin molding, but it is preferable to subsequently subject it to a melt filtering step or a pelletizing step.
- the method of the present invention preferably further includes a step of filtering the melted resin containing the alicyclic structure-containing polymer in a molten state.
- the molten resin may be obtained from a solvent removal step (if the resin is obtained in a molten state) or a melting step.
- Melt filtration may be performed using, for example, a leaf disk type filter or a candle type filter.
- the mesh size of the filter may be, for example, 40 ⁇ m or less, preferably 20 ⁇ m or less, preferably 10 ⁇ m or less.
- the melt filtration differential pressure may be, for example, 7 MPa or less, preferably 5 MPa or less, more preferably 3 MPa or less.
- the differential pressure refers to the differential pressure at the time of the highest differential pressure during filtration.
- non-melting foreign matter e.g. resin deterioration components such as scorch components
- the differential pressure of melt filtration is equal to or less than the above upper limit, the load on the equipment can be reduced, and the life of the equipment can be extended.
- the differential pressure (B) of melt filtration is larger than the differential pressure (A) of solution filtration.
- the upper limit of the difference (BA) between the differential pressure of solution filtration (A) and the differential pressure of melt filtration (B) is, for example, 6.5 MPa or less, preferably 6 MPa or less, and more preferably 5 MPa or less. There may be.
- the difference (BA) between the differential pressure (A) in solution filtration and the differential pressure (B) in melt filtration has a lower limit of, for example, 0.3 MPa or more, preferably 0.5 MPa or more, more preferably 1.5 MPa or more. It may be 0 MPa or more.
- differential pressure difference (BA) is equal to or greater than the lower limit, the foreign matter removal rate and solution filtration rate during solution filtration are improved, and the foreign matter removal rate and melt filtration rate are further improved during melt filtration. can be done. If the differential pressure difference (BA) is equal to or less than the upper limit, the load on the equipment is reduced, and the life of the equipment can be extended.
- the method of the present invention preferably further includes a step of pelletizing the melted resin containing the alicyclic structure-containing polymer to obtain pelletized resin as a recycled product.
- the molten resin may be obtained from a solvent removal step (if the resin is obtained in a molten state), a melting step, or a melt filtration step.
- a method for obtaining a pelletized resin (regenerated pellets) is not particularly limited, and any known method can be employed. For example, there is a method of extruding the resin obtained by heat-melting the above molded article into a strand (rod) from a strand die in a molten state, cooling the strand, cutting the strand with a strand cutter, and pelletizing the strand.
- the temperature at which the molded body is melted is preferably Tg + 60 (°C) to Tg + 180 (°C), more preferably Tg + 90 (°C) to Tg + 160 (°C), where Tg (°C) is the glass transition temperature of the polymer resin having an alicyclic structure. °C). If the temperature is too low, the resulting regenerated pellets may become non-uniform due to high viscosity. On the other hand, if the temperature is too high, the resin and compounding agents may deteriorate, and the melt flow rate and yellowness of the resulting recycled pellets may largely change from those of the resin molded product before reuse.
- Strand cutting methods include, for example, the “cold cut method” in which a rod-shaped strand extruded from a die hole is solidified by water cooling and cut, and the “hot cut method” in which the strand is cut immediately after being extruded from the die hole. There are other methods, and any of them can be applied.
- the shape of the regenerated pellets is usually circular or elliptical in cross section (perpendicular to the direction of strand discharge), but can be formed into any shape by the hole shape of the forming die.
- the average diameter of the pellet cross section is usually 0.1 to 10 mm, preferably 0.5 to 5 mm, more preferably 1 to 4 mm.
- the length of the pellet (the length in the strand discharge direction) can be arbitrarily changed depending on the strand cutting speed, but is usually 1 to 10 mm, preferably 2 to 8 mm, more preferably 2 to 6 mm.
- the method of the present invention is a resin containing an alicyclic structure-containing polymer obtained in any of the above steps (e.g., pelletized resin, resin in a molten state) or an alicyclic polymer as a recycled product from a polymer solution. It is preferable to further include a step of forming a resin molding containing the structure-containing polymer.
- the resin obtained in any of the above processes includes the pelletized resin obtained in the pelletizing process, the solvent removal process (when the resin is obtained in a molten state), the melting process, or the melt obtained in the melt filtration process. state resins.
- Examples of the polymer solution obtained in any of the above steps include the polymer solution obtained in the dissolution step (when the adsorbent addition step is not performed), the solution filtration step, or the antioxidant addition step.
- the formation of a resin molded body is performed, for example, by melt extrusion molding of a resin (e.g., pelletized resin), or by pouring a molten resin into a molding machine (e.g., a mold), by extrusion molding of a molten resin, or by extruding a molten resin. into a molding machine (eg, mold), or by pouring the polymer solution into a molding machine (eg, mold) followed by solvent removal (eg, drying).
- a resin e.g., pelletized resin
- a molding machine e.g., a mold
- solvent removal e.g., drying
- the recycled molded product forming step may be performed by molding the recycled pellets into a film.
- the method for molding the regenerated pellets into a film is not limited, and for example, either a melt molding method or a solution casting method may be used.
- the melt molding method includes, for example, an extrusion molding method for molding by melt extrusion, a press molding method, an inflation molding method, an injection molding method, a blow molding method, and a stretch molding method.
- the extrusion molding method by melt extrusion molding is preferable from the viewpoint that a film excellent in mechanical strength and surface precision can be obtained. According to the manufacturing method of the present invention, even in an extrusion molding method that undergoes a heat history due to heating and melting, the generation of foreign matter is suppressed, and an optical film with a small content of foreign matter can be obtained.
- the extrusion molding method is a method in which a resin is heated and melted in an extruder and then extruded through a flat die to continuously obtain a film-shaped molded product.
- the extruder heats and kneads the resin and extrudes the melt in the form of a film through a die at a constant extrusion rate.
- the extruded melt is taken up by rolls rotating at a constant speed, cooled and molded.
- the roll temperature, layout, etc. are not particularly limited.
- Flat dies include T dies, coat hanger dies, fish tail dies, and the like, depending on the structure of the resin distribution channel.
- the thickness of the resulting optical film can be adjusted by adjusting the extruded resin temperature and pressure, and by fine-tuning the gap between the lips through which the molten resin is extruded.
- the temperature of the extruded resin is usually 80° C. to 180° C. higher than the glass transition temperature of the recycled pellets.
- the gap between the lips can be adjusted using the choke bar and the choke bar adjusting bolt.
- the thickness of the optical film to be obtained varies depending on the type and application of the optical film, but is usually 10 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, and usually 700 ⁇ m or less, preferably 500 ⁇ m or less. More preferably, it is 300 ⁇ m or less.
- the optical film obtained by the production method of the present invention may be a stretched optical film obtained by subjecting the optical film obtained above to further stretching treatment.
- a known stretching treatment such as uniaxial stretching, biaxial stretching, or oblique stretching can be appropriately employed.
- the stretching method is not particularly limited, but includes roll and float longitudinal stretching, tenter transverse uniaxial stretching, simultaneous biaxial stretching and oblique stretching.
- the temperature at which the unstretched film is stretched is preferably between Tg+2°C and Tg+30°C, more preferably between Tg+5°C and Tg+25°C, where Tg is the glass transition temperature of the regenerated pellets.
- the draw ratio is usually 1.01 to 30 times, preferably 1.01 to 10 times, more preferably 1.01 to 5 times.
- the optical film obtained by the production method of the present invention has a low content of foreign matter, it can be suitably used for the production of optical members in display devices such as liquid crystal display devices and electroluminescence display devices.
- the optical film can be used as a retardation film, a protective film for a polarizing plate, a polarizing film, a brightness enhancement film, a light diffusion film, a light collecting film, a reflective film, and the like in display devices and optical members.
- a sample was prepared by heating and dissolving a measurement sample in cyclohexane at 40° C. so that the sample concentration was 4 mg/mL.
- the measurement was performed by connecting three columns of TSKgelG5000HXL, TSKgelG4000HXL, and TSKgelG2000HXL manufactured by Tosoh Corporation in series, under the conditions of a flow rate of 1.0 mL/min, a sample injection amount of 100 ⁇ mL, and a column temperature of 40°C.
- Tg Glass transition temperature
- ⁇ Dissolution time> (If the melting time is long, the production cycle is bad.) Time required for 100 g of sample after pulverization to dissolve. Check if the set concentration is achieved with the prescribed solvent composition and 100 rotations of AG stirring. Samples were taken at each time, dried in a vacuum drying oven at 120°C for 12 hours, and dissolved concentration was confirmed. ⁇ : Less than 0.5 hours ⁇ : 0.5 hours to less than 1.0 hours ⁇ : 1 hour or more
- ⁇ Yellowness index ( ⁇ Yi)> (If the value is high, the yellow color is too strong and cannot be used as a product, and the resin may deteriorate due to oxidation.)
- the pellets were injection-molded at a cylinder temperature of 200 to 300° C. to prepare a plate with a thickness of 3 mm.
- the degree of yellowness (hereinafter referred to as ⁇ Yi) of the plate was measured with a spectral color difference meter (manufactured by Nippon Denshoku Industries, model: SE2000) capable of measuring an XYZ color system.
- B The number of foreign substances with a size of 3 ⁇ m or more is 11 or more and 29 or less.
- C The number of foreign matters with a size of 3 ⁇ m or more is 30 or more and 99 or less.
- D The number of foreign particles with a size of 3 ⁇ m or more is 100 or more.
- MTF 0 3,8 ]tetradeca-3,5,7,12-tetraene
- MTF weight ratio 52/38/10 7 parts (1% by weight based on the total amount of monomers used for polymerization ) and 1600 parts of cyclohexane, 0.55 parts of tri-i-butylaluminum and 0.21 parts of isobutyl alcohol, 0.84 parts of diisopropyl ether as a reaction modifier, and 3.24 parts of 1-hexene as a molecular weight modifier. added. 24.1 parts of 0.65% tungsten hexachloride solution dissolved in cyclohexane was added thereto and stirred at 55° C. for 10 minutes.
- the hydrogen conversion rate of the ring-opening polymer hydrogenated product was 99.9%.
- the solution is treated with a cylindrical concentrator dryer (manufactured by Hitachi, Ltd.) at a temperature of 270 ° C. and a pressure of 1 kPa or less to remove cyclohexane as a solvent and other volatile components from the solution, thereby obtaining a polymer in a molten state.
- a cylindrical concentrator dryer manufactured by Hitachi, Ltd.
- pellets A of the ring-opening polymer hydrogenated ring-opening type alicyclic raw material It was obtained as a structure-containing polymer resin (ring-opening polymer resin).
- the weight average molecular weight (Mw) of the hydrogenated ring-opening polymer constituting the pellet A was 38,000, the molecular weight distribution (Mw/Mn) was 2.5, Tg was 129°C, and ⁇ Yi was 0.35.
- DCP units DCP-derived structural unit
- TCD-derived structural units TCD units
- MTF-derived structural units MTF-derived structural units
- Raw material base film (creation of stretched film) >> The wound and collected sheet is attached to a stretching device installed in the same clean room as the roll, heated to 139 ° C. (Tg + 10 ° C.) with a heating roll, and then the first roll and the second roll having different rotation speeds. The sheet was uniaxially stretched in the extrusion direction at a draw ratio of 2.0 and at a drawing speed (pulling speed) of 15 mm/sec while passing through rolls in order to obtain a stretched film A as a raw material base film.
- Tg + 10 ° C. The sheet was uniaxially stretched in the extrusion direction at a draw ratio of 2.0 and at a drawing speed (pulling speed) of 15 mm/sec while passing through rolls in order to obtain a stretched film A as a raw material base film.
- the pulverized material is placed on a belt conveyor and sent to a dissolution tank, and a mixed solvent of 93% cyclohexane (freezing point 6.5 ° C., boiling point 81.4 ° C.) and 7% methylcyclohexane (freezing point -126 ° C., boiling point 100 ° C.)
- a mixed solvent 93% cyclohexane (freezing point 6.5 ° C., boiling point 81.4 ° C.) and 7% methylcyclohexane (freezing point -126 ° C., boiling point 100 ° C.)
- Add 17.6 parts of pulverized film (concentration 15%) to 100 parts, add 0.53 parts of acidic clay (manufactured by Mizusawa Chemical Industry Co., Ltd., product name "Mizuka Ace #20") as an adsorbent, and heat at 70 ° C. for 2 hours. Stirred for more than an hour.
- pellets B of the hydrogenated ring-opening polymer were obtained as a regenerated alicyclic structure-containing polymer resin.
- the dissolution time of the film pulverized material, the degree of adhesion (deposit) to the exit of the die after extrusion molding, the degree of foreign matter generation of pellet B, and ⁇ Yi of pellet B were evaluated.
- Example 2 The procedure was carried out in the same manner as in Example 1, except that 23.5 parts (concentration: 19%) of the pulverized film was added to 100 parts of the mixed solvent when dissolving the pulverized film in the mixed solvent.
- Example 3 As the mixed solvent, a mixed solvent of 93% cyclohexane and 7% toluene (freezing point ⁇ 93° C., boiling point 111° C.) (Example 3), a mixed solvent of 98% cyclohexane and 2% methylcyclohexane (Example 4), or cyclohexane 81 %, and 19% methylcyclohexane (Example 6), but the same procedure as in Example 1 was performed.
- Example 5 The procedure was carried out in the same manner as in Example 1, except that a base film without an easy-adhesion layer (polyurethane layer) was used as the raw material molded body.
- a base film without an easy-adhesion layer polyurethane layer
- Example 7 The procedure was the same as in Example 1, except that melt filtration was not performed.
- Example 8 Activated clay (Mizusawa Chemical Industry Co., Ltd. product name "Galeon Earth”, Example 8) or activated alumina (Sumitomo Alchem Co., Ltd. product name "A-11", Example 9) was used as an adsorbent, except for using As in Example 1.
- Example 10 The procedure of Example 1 was repeated except that the film pulverized material was collected through a punching plate with 20 mm holes.
- Example 11 Example 1 except that in the production of the raw material molded product, the copolymer B (raw material addition type alicyclic structure-containing polymer resin) prepared in Production Example 2 below was used instead of the ring-opening polymer resin for the raw material. went as well.
- the copolymerization reaction was stopped by adding isopropyl alcohol. After depressurization, the polymer solution was taken out and then brought into contact with an aqueous solution of 5 liters of concentrated hydrochloric acid to 1 m 3 of water with strong stirring at a ratio of 1:1 to transfer the catalyst residue to the aqueous phase. After this contact mixture was allowed to stand, the aqueous phase was separated and removed, and the mixture was washed with water twice to purify and separate the polymerization liquid phase.
- the purified and separated polymerization liquid phase was brought into contact with 3 times the amount of acetone under strong stirring to precipitate the copolymer, and then the solid portion (copolymer) was collected by filtration and thoroughly washed with acetone. . Furthermore, in order to extract unreacted monomers, this solid portion was put into acetone so as to be 40 kg/m 3 and then subjected to extraction at 60° C. for 2 hours. After the extraction treatment, the solid portion was collected by filtration and dried at 130° C. and 350 mmHg for 12 hours under a stream of nitrogen to obtain an ethylene/norbornene copolymer (copolymer B).
- An ethylene/norbornene copolymer (copolymer B) was pelletized in the same manner as the ring-opening polymer hydrogenated pellet A was prepared in Production Example 1 A-1-2.
- the pelletized ethylene/norbornene copolymer (copolymer B) had a weight average molecular weight (Mw) of 96,000, a molecular weight distribution (Mw/Mn) of 2.4, and a Tg of 138°C.
- Example 1 The procedure of Example 1 was repeated except that a mixed solvent of 99% cyclohexane and 1% methylcyclohexane (Comparative Example 1) or a mixed solvent of 78% cyclohexane and 22% methylcyclohexane (Comparative Example 2) was used as the mixed solvent. rice field.
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Abstract
Description
本発明の樹脂成形体の再利用方法(以下、「本発明の方法」という。)は、脂環式構造含有重合体を含む樹脂成形体を粉砕して成形体粉砕物を得る工程(「粉砕工程」)、および成形体粉砕物を、混合溶媒100重量%に対して80重量%以上98重量%以下のシクロヘキサンと、2重量%以上20重量%以下の凝固点-40℃以下の炭化水素系または芳香族系の溶剤とを含む混合溶媒に溶解して重合体溶液を得る工程(「溶解工程」)を含むことを特徴とする。本発明の方法は、以下の工程のいずれか1以上をさらに含んでもよい:
・樹脂成形体を粉砕する工程と成形体粉砕物を溶解する工程との間に、成形体粉砕物を篩がけする工程(篩がけ工程);
・成形体粉砕物溶解系に吸着剤を添加する工程(吸着剤添加工程);
・重合体溶液を溶液状態でろ過して異物、吸着剤を除去する工程(溶液ろ過工程);
・ろ過した重合体溶液に酸化防止剤を添加する工程(酸化防止剤添加工程);
・重合体溶液から混合溶媒を除去して脂環式構造含有重合体を含む樹脂を回収する工程(溶媒除去工程);
・溶媒除去工程で回収した樹脂を溶融する工程(溶融工程);
・溶融した樹脂を溶融状態でろ過する工程(溶融ろ過工程);
・溶融した樹脂をペレット化して再生品としてのペレット化樹脂を得る工程(ペレット化工程);および
・上記いずれかの工程で得られた、樹脂(例、ペレット化樹脂、溶融状態の樹脂)または重合体溶液から再生品としての樹脂成形体を形成する工程(成形体形成工程)。
本発明の方法において、原料および再生品としての樹脂成形体の成分となる脂環式構造含有重合体は、主鎖及び/又は側鎖に脂環式構造を有するものであり、機械強度、耐熱性などの観点から、主鎖に脂環式構造を含有するものが好ましい。
ノルボルネン系重合体としては、具体的にはノルボルネン系モノマーの開環重合体、ノルボルネン系モノマーと開環共重合可能なその他のモノマーとの開環共重合体、及びそれらの水素添加物、ノルボルネン系モノマーの付加重合体、ノルボルネン系モノマーと共重合可能なその他のモノマーとの付加共重合体などが挙げられる。これらの中でも、透明性の観点から、ノルボルネン系モノマーの開環(共)重合体水素添加物が最も好ましい。
上記の脂環式構造を有する重合体は、例えば特開2002-321302号公報などに開示されている公知の重合体から選ばれる。
再利用に供する成形体としては、レンズ、プリズム、光学フィルム、光学シート、光ディスク基板、導光板、ライトガイド、光ファイバー、ミラー等の光学用途の成形体;ディスポーザブルシリンジ、薬液バイヤル、薬品包装用フィルム、検査セル、検査容器、輸液バッグ、シリンジ用ロッド等の医療用の成形体;電線被覆、ウェハーシッパー、コンデンサーフィルム、回路基板、コネクターなどのシート、フィルム、板材、容器、絶縁材等の電気又は電子用途の成形体;板材、パイプ、丸棒、ボトル、建材、文具等が挙げられる。再利用に供する成形体は、例えば、成形体の廃材、成形体を製造する際に生じる加工廃材(例、フィルムの耳、型抜きの残り)、使用済みの成形体であってもよい。再利用に供する成形体は、合成した樹脂(バージン材)に由来する成形体であってもよく、再利用した樹脂(再生品)に由来する成形体であってもよい。再利用に供する成形体が、成形体が平面形状を有する場合、成形体の厚さは、例えば30μm以上、好ましくは40μm以上、より好ましくは50μm以上であってもよく、例えば100μm以下、好ましくは90μm以下、より好ましくは80μm以下であってもよい。
本発明の方法は、原料となる樹脂成形体を粉砕して成形体粉砕物を得る工程を含む。樹脂成形体の粉砕は、例えば、粉砕機、裁断機を用いて行うことができる。樹脂成形体を粉砕することにより、樹脂成形体の溶解時間を短縮化して溶解効率を向上することができ、このことにより、再生品の外観欠点をより少なく抑制させて色調などの物性を向上させること、およびプロセス時間の短縮化に寄与することができる。
本発明の方法は、樹脂成形体を粉砕する工程と成形体粉砕物を溶解する工程との間に、成形体粉砕物を所定の孔径(φ)の篩で篩がけする工程をさらに含むことが好ましい。所定の孔径としては、例えば3mm以上、好ましくは4mm以上、より好ましくは5mm以上であってもよく、例えば15mm以下、好ましくは12mm以下、より好ましくは10mm以下であってもよい。成形体を上記上限以下の径の篩で篩がけして、溶解に供する成形体粉砕物のサイズを小さいものとすることにより、溶解時間をより短縮化させて溶解効率が向上し、再生品の外観欠点をより少なく抑制させて色調などの物性を向上させること、およびプロセス時間の短縮化に寄与することができる。また、篩の径を上記下限以上とすることにより、篩を通過しない成形体粉砕物による回収効率の低下を抑制することができる。
本発明の方法は、成形体粉砕物を溶媒に溶解する工程を含む。成形体粉砕物を溶媒に溶解することにより、成形体粉砕物からの不溶性異物(例、ヤケ成分等の樹脂劣化成分、ウレタン等の塗布物)の除去(例、溶液ろ過による除去)および溶解性異物(例、酸化防止剤の変質物)の除去(例、吸着による除去)を容易にすることができる。溶媒は、混合溶媒100重量%に対して80重量%以上98重量%以下のシクロヘキサンと2重量%以上20重量%以下の凝固点-40℃以下の炭化水素系または芳香族系の溶剤を含む混合溶媒である。溶剤の凝固点は、-40℃以下である。溶剤の凝固点は、例えば、示差走査熱量計による結晶化温度を読み取ることによって測定することができる。あるいは、上記の凝固点を有する溶剤を、物性値が開示された溶媒用化合物から適宜選択してもよい。凝固点が低い溶剤を含む混合溶媒を用いることにより、温度環境に関わらず、例えば冬季等の寒冷環境下でも溶媒や重合体溶液の凝固が防止され、重合体溶液の溶解状態が良好となり、再生品の外観欠点をより少なく抑制させ、色調などの物性を向上させることができる。
本発明の方法は、成形体粉砕物溶解系に吸着剤を添加する工程をさらに含むことが好ましい。「成形体粉砕物溶解系に吸着剤を添加する」こととして、吸着剤は、重合体溶液と接触するように添加されていればよく、例えば、重合体溶液に添加されてもよく、成形体粉砕物の溶解に用いられる混合溶媒に添加されてもよく、成形体粉砕物と一緒に混合溶媒に添加されてもよく、溶解に用いられる容器にあらかじめ添加されてもよい。吸着剤の添加により、重合体溶液中の異物(例、酸化防止剤の変質物等の溶解性異物)を吸着して除去することができ、再生品の外観欠点をより少なく抑制させて色調などの物性を向上させることに寄与することができる。このような吸着剤としては、例えば、酸性白土、活性白土、活性アルミナ、およびゼオライトが挙げられる。これらの吸着剤は、酸化防止剤の変質物等の溶解性異物を良好に吸着することができる。吸着剤の量は、混合溶媒100重量部に対して、例えば2.0重量部以上、好ましくは2.5重量部以上、より好ましくは3.0重量部以上であってもよく、例えば5.0重量部以下、好ましくは4.5重量部以下、より好ましくは4.0重量部以下であってもよい。
本発明の方法は、重合体溶液を溶液状態でろ過して異物、吸着剤を除去する工程をさらに含むことが好ましい。この工程により、溶液状態でのろ過(溶液ろ過)により、不溶性異物(例、ウレタン等の、脂環式構造含有重合体以外の追加の材料)、吸着剤、および吸着剤に吸着した溶解性異物(例、酸化防止剤の変質物)を除去することができ、再生品の外観欠点をより少なく抑制させて色調などの物性を向上させることに寄与することができる。溶液ろ過は、濾過助剤を濾過床として用いて行ってもよい。濾過助剤としては、例えば、珪藻土(例、商品名「ラヂオライト」)、パーライト(例、商品名「トプコ」)が挙げられる。
本発明の方法は、ろ過した重合体溶液に酸化防止剤を添加する工程をさらに含むことが好ましい。通常、再利用される樹脂成形体には酸化防止剤が配合されており、当該酸化防止剤の少なくとも一部は、樹脂成形体の使用中に変質していることがある。そのため、この工程により、変質によって消失した酸化防止剤を補充することができる。酸化防止剤としては、一般的な脂環式構造含有重合体樹脂用酸化防止剤を用いることができ、例えば、フェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤などが挙げられるが、これらの中でも、フェノール系酸化防止剤が好ましく、アルキル置換フェノール系酸化防止剤が特に好ましく用いられる。
本発明の方法は、重合体溶液から混合溶媒を除去して脂環式構造含有重合体を含む樹脂を回収する工程をさらに含むことが好ましい。混合溶媒の除去は、例えば、混合溶媒を乾燥させることにより行うことができる。混合溶媒の乾燥は、例えば、加熱乾燥、減圧乾燥、または加熱減圧乾燥で行ってもよい。加熱乾燥または加熱減圧乾燥を行う温度は、混合溶媒を除去することができる限りにおいて特に限定されないが、例えば250℃以上、好ましくは260℃以上、より好ましくは270℃以上であってもよく、例えば320℃以下、好ましくは310℃以下、より好ましくは300℃以下であってもよい。減圧乾燥または加熱減圧乾燥を行う圧力は、大気圧より低い圧力であり、例えば-90kPa以下、好ましくは-95kPa以下、より好ましくは-100kPa以下であってもよい。加熱乾燥または加熱減圧乾燥を行う場合、樹脂は溶融状態で回収されてもよい。なお、回収された樹脂は、そのまま再生品樹脂として再生品樹脂成形体の成形に供してもよいが、引き続き溶融工程や溶融ろ過工程に供することが好ましい。
本発明の方法は、溶媒除去工程で回収した脂環式構造含有重合体を含む樹脂を溶融する工程をさらに含むことが好ましい。溶融は、回収した樹脂を加熱することにより行うことができる。溶融を行う温度は、脂環式構造含有重合体の種類により適宜決定することができるが、例えば250℃以上、好ましくは260℃以上、より好ましくは270℃以上であってもよく、例えば320℃以下、好ましくは310℃以下、より好ましくは300℃以下であってもよい。なお、溶媒除去工程において、例えば加熱乾燥または加熱減圧乾燥により行うことにより、樹脂が溶融状態となる場合、溶媒除去工程は、溶融工程も兼ねることになる。溶融工程で得られた溶融状態の樹脂は、そのまま再生品樹脂として再生品樹脂成形体の成形に供してもよいが、引き続き溶融ろ過工程やペレット化工程に供することが好ましい。
本発明の方法は、溶融した脂環式構造含有重合体を含む樹脂を溶融状態でろ過する工程をさらに含むことが好ましい。溶融した樹脂は、溶媒除去工程(樹脂が溶融状態で得られる場合)または溶融工程で得られたものを用いてもよい。溶融ろ過は、例えば、リーフディスク型フィルター、キャンドル型フィルターをフィルターとして行ってもよい。フィルターのメッシュ径は、例えば40μm以下、好ましくは20μm以下、好ましくは10μm以下であってもよい。溶融ろ過の差圧は、例えば7MPa以下、好ましくは5MPa以下、より好ましくは3MPa以下であってもよい。なお、差圧は、ろ過時の最も高い差圧時の差圧をいう。溶融ろ過工程を行うことにより、非溶融性異物(例、ヤケ成分等の樹脂劣化成分)を除去することができ、再生品の外観欠点をより少なく抑制させて色調などの物性を向上させることに寄与することができる。溶融ろ過の差圧が上記上限以下であれば、設備への負荷が低減され、設備の寿命を向上させることができる。また、溶液ろ過工程と溶融ろ過工程との両方を行う場合、溶融ろ過の差圧(B)は、溶液ろ過の差圧(A)よりも大きいことが好ましい。この場合、溶液ろ過の差圧(A)と溶融ろ過の差圧(B)の差(B-A)は、上限については、例えば6.5MPa以下、好ましくは6MPa以下、より好ましくは5MPa以下であってもよい。また、溶液ろ過の差圧(A)と溶融ろ過の差圧(B)の差(B-A)は、下限については、例えば0.3MPa以上、好ましくは0.5MPa以上、より好ましくは1.0MPa以上であってもよい。上記差圧の差(B-A)が上記下限以上であれば、溶液ろ過時の異物除去率と溶液ろ過速度を向上させつつ、溶融ろ過時の異物除去率と溶融ろ過速度も更に向上させることができる。上記差圧の差(B-A)が上記上限以下であれば、設備への負荷が低減され、設備の寿命を向上させることができる。
本発明の方法は、溶融した脂環式構造含有重合体を含む樹脂をペレット化して再生品としてのペレット化樹脂を得る工程をさらに含むことが好ましい。溶融した樹脂は、溶媒除去工程(樹脂が溶融状態で得られる場合)、溶融工程、または溶融ろ過工程で得られたものを用いてもよい。ペレット化樹脂(再生ペレット)を得る方法は特に限定されず、公知の方法をいずれも採用できる。例えば、上記の成形体を加熱溶融した樹脂を、溶融状態でストランドダイからストランド(棒)状に押し出して冷却した後、ストランドカッターで切断してペレット化する方法が挙げられる。
本発明の方法は、上記いずれかの工程で得られた、脂環式構造含有重合体を含む樹脂(例、ペレット化樹脂、溶融状態の樹脂)または重合体溶液から再生品としての脂環式構造含有重合体を含む樹脂成形体を形成する工程をさらに含むことが好ましい。上記いずれかの工程で得られた樹脂としては、ペレット化工程で得られたペレット化樹脂、溶媒除去工程(樹脂が溶融状態で得られる場合)、溶融工程、または溶融ろ過工程で得られた溶融状態の樹脂が挙げられる。上記いずれかの工程で得られた重合体溶液としては、溶解工程(吸着剤添加工程を行わない場合)、溶液ろ過工程、または酸化防止剤添加工程で得られた重合体溶液が挙げられる。樹脂成形体の形成は、例えば、樹脂(例、ペレット化樹脂)の溶融押出し成形または樹脂を溶融して成形機(例、型)に流し込むこと、溶融状態の樹脂の押出し成形または溶融状態の樹脂を成形機(例、型)に流し込むこと、あるいは、重合体溶液を成形機(例、型)に流し込んだ後溶媒除去(例、乾燥)することにより形成してもよい。
そして、実施例および比較例において、各測定項目および評価項目は、以下の方法で測定または評価した。
重量平均分子量(Mw)および数平均分子量(Mn)は、シクロヘキサンを溶離液とするゲルパーミエーションクロマトグラフィ(GPC)による標準ポリイソプレン換算値として40℃において測定した。測定装置としては、東ソー社製HLC8120GPCを用いた。
標準ポリイソプレンとしては、東ソー社製標準ポリイソプレン、Mw=602、1390、3920、8050、13800、22700、58800、71300、109000、280000の計10点を用いた。
サンプルは、サンプル濃度4mg/mLになるように、40℃にて測定試料をシクロヘキサンに加熱溶解させて調製した。
測定は、カラムとして東ソー社製TSKgelG5000HXL、TSKgelG4000HXL、TSKgelG2000HXL計3本直列に繋いで用い、流速1.0mL/分、サンプル注入量100μmL、カラム温度40℃の条件で行った。
溶媒として重クロロホルム/四塩化炭素の混合溶液(1/1重量比)を用いて、1H-NMRスペクトルにより測定した。
示差走査熱量分析計を用いて、JISK6911に基づいて測定した。
(溶解時間が長いと、生産サイクルが悪い)
粉砕後のサンプル100gが溶解する時間。
所定の溶剤組成、AG攪拌100回転で、設定した濃度になるかを確認。
各時間でサンプリングし、減圧乾燥オーブン120℃で12時間乾燥させ、溶解している濃度を確認した。
◎:0.5時間未満
〇:0.5時間から1.0時間未満
△:1時間以上
(個数が多いと製品として使用不可)
ペレット500g中の異物数を目視とマイクロスコープ(KEYENCE製 VHX-2000)で確認した。
異物サイズは異物の長辺を測定。
◎:0個
〇:2個以下
×:3個以上
(値が高いと製品として使用不可、異物混入の原因の一つ)
4時間で0.3mm以上の目ヤニが付着しているダイ穴数の割合(全体の穴数に対する付着した穴数)をノギスを用い目視確認した。
1つの穴から出る樹脂量は、4時間で、150~200kg(穴数は40個)
◎:10%未満
〇:10%以上 30%未満
×:30%以上
(値が高いと黄色が強く製品として使用不可、樹脂酸化劣化がある)
ペレットを日精樹脂工業製 NS20-2A型を用い、シリンダー温度200~300℃の範囲で射出成型して、3mm厚の板を作製した。
XYZ表色系が測定可能な分光色差計(日本電色工業製 型式:SE2000)で、板の黄色度(以下、ΔYi)の測定を行った。
◎:0.5未満
〇:0.5以上~0.7未満
×:0.7以上
(個数が多いと製品として使用不可)
外観欠点は、コンピュータ制御落射蛍光顕微鏡(オリンパス社製、BX61-FL)を用い、BV励起(435nm)、倍率200倍で観察した。フィルムを顕微鏡に置き、1cm×1cmの視野にある蛍光を発する異物の個数を1cm2当たりの異物個数として求めた(体積:0.4cm3)。更に、異物の大きさによっても分類し、下記の基準に従い評価した。
A:大きさが3μm以上の異物の個数が10個以下である。
B:大きさが3μm以上の異物の個数が11個以上、29個以下である。
C:大きさが3μm以上の異物の個数が30個以上、99個以下ある。
D:大きさが3μm以上の異物の個数が100個以上である。
<A-1.原料用開環型脂環式構造含有重合体樹脂の調製>
<<A-1-1.開環重合>>
窒素で置換した反応器に、トリシクロ[4.3.0.12,5]デカ-3-エン(以下、「DCP」という)とテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン(以下、「TCD」という)とテトラシクロ[9.2.1.02,10.03,8]テトラデカ-3,5,7,12-テトラエン(以下、「MTF」という)の混合物(重量比52/38/10)7部(重合に使用するモノマー全量に対して重量1%)とシクロヘキサン1600部を加え、トリ-i-ブチルアルミニウム0.55部とイソブチルアルコール0.21部、反応調整剤としてジイソプロピルエーテル0.84部、及び分子量調節剤として1-ヘキセン3.24部を添加した。ここに、シクロヘキサンに溶解させた0.65%の六塩化タングステン溶液24.1部を添加して、55℃で10分間攪拌した。次いで、反応系を55℃に保持しながら、DCPとTCDとMTF(重量比52/38/10)の混合物を693部とシクロヘキサンに溶解させた0.65%の六塩化タングステン溶液48.9部とをそれぞれ系内に150分かけて連続的に滴下した。その後、30分間反応を継続し重合を終了した。
重合終了後、ガスクロマトグラフィーにより測定したモノマーの重合転化率は重合終了時で100%であった。
得られた開環重合反応液を耐圧性の水素化反応器に移送し、ケイソウ土担持ニッケル触媒(クラリアント触媒社製、製品名「T8400RL」、ニッケル担持率57%)1.4部及びシクロヘキサン167部を加え、180℃、水素圧4.6MPaで6時間反応させた。この反応溶液を、ラヂオライト#500を濾過床として、圧力0.25MPaで加圧濾過(石川島播磨重工社製、製品名「フンダフィルター」)して水素化触媒を除去し、無色透明な溶液を得た。次いで前記水素添加物100部あたり0.5部の酸化防止剤:ペンタエリスリトールテトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート](チバ・スペシャルティ・ケミカルズ社製、製品名「イルガノックス1010」)を、得られた溶液に添加して溶解させた。次いで、ゼータープラスフィルター30H(キュノーフィルター社製、孔径0.5~1μm)にて順次濾過しさらに別の金属ファイバー製フィルター(孔径0.4μm、ニチダイ社製)にて濾過して微小な固形分を除去した。開環重合体水素添加物の水素転化率は99.9%であった。
次いで、上記溶液を、円筒型濃縮乾燥器(日立製作所社製)を用いて、温度270℃、圧力1kPa以下で、溶液から、溶媒であるシクロヘキサン及びその他の揮発成分を除去し、溶融状態のポリマーを270℃でポリマーフィルター(富士フィルター製)を通して、濃縮機に直結したダイから溶融状態でストランド状に押出し、冷却後、開環重合体水素添加物のペレットAを原料用開環型脂環式構造含有重合体樹脂(開環重合体樹脂)として得た。ペレットAを構成する開環重合体水素添加物の重量平均分子量(Mw)は38,000、分子量分布(Mw/Mn)は2.5、Tgは129℃、ΔYiは0.35であった。
尚、開環重合体合成時の重合転化率が100%であり、水素転化率も99.9%と高水準であることから、開環重合体水素添加物中の、DCP由来の構造単位(DCP単位)、TCD由来の構造単位(TCD単位)、及びMTF由来の構造単位(MTF単位)は、開環重合体の製造に用いたモノマーの使用量に等しいと推定される。
<<A-2-1.原料用未延伸フィルムの作成>>
得られたペレットAを、空気を流通させた熱風乾燥器を用いて70℃で2時間乾燥して水分を除去した後、65mmφのスクリューを備えた樹脂溶融混練機を有するTダイ式フィルム溶融押出し成形機(Tダイ幅500mm)を使用し、クラス10,000以下のクリーンルーム内で、溶融樹脂温度229℃、Tダイ温度229℃の成形条件にて、厚さ100μm、幅500mmの未延伸フィルムAのシートを押出し成形した。得られたシートはロールに巻き取り回収した。
巻き取り回収した上記シートを、ロールごと上記と同一のクリーンルーム内に設置された延伸装置に取り付け、加熱ロールにて139℃(Tg+10℃)に加熱した後、回転速度の異なる第一ロール、第二ロールの順に通過させながら、シートを押出方向に2.0倍の延伸倍率で、延伸速度(引っ張り速度)15mm/秒にて一軸延伸し、延伸フィルムAを原料基材フィルムとして得た。
ポリエーテル系ポリウレタンの水分散体(第一工業製薬社製「スーパーフレックス150HS」)をポリウレタンの量で100部と、架橋剤としてエポキシ化合物(ナガセケムテックス社製「デナコールEX313」)15部と、滑材としてシリカ粒子の水分散液(日産化学社製「スノーテックスMP1040」;平均粒子径120nm)をシリカ粒子の量で8部及びシリカ粒子の水分散液(日産化学社製「スノーテックスXL」;平均粒子径50nm)をシリカ粒子の量で8部と、濡れ剤としてアセチレン系界面活性剤(エアープロダクツアンドケミカルズ社製「サーフィノール440」)を固形分合計量に対して0.5重量%と、水とを配合して、固形分濃度2%の液状の樹脂組成物1(塗布用ポリウレタン樹脂組成物)を得た。
コロナ処理装置(春日電機社製)を用いて、出力300W、電極長240mm、ワーク電極間3.0mm、搬送速度4m/minの条件で、上記A-2-2で得た延伸フィルムA(基材フィルム)の表面に放電処理を施した。延伸フィルムAの放電処理を施した表面に、前記の液状の樹脂組成物1を、乾燥厚みが0.1μmになるようにロールコーターを用いて塗布した。その後、温度130℃で60秒間加熱して、基材フィルム上に易接着層(ポリウレタン層)を形成した。これにより、基材フィルム及び易接着層を備える複層フィルムを原料成形体として得た。複層フィルムをスリット加工することによりフィルムの両端部が分離され、得られたフィルムの両端部は、ロールに巻取り回収した。
<1-1.原料成形体からの開環重合体樹脂の回収>
巻取り回収したフィルムの両端部を、粉砕機により粉砕し、5mm穴の篩(パンチングプレート)を通しフィルム粉砕物を回収した。粉砕物は、ベルトコンベアーに載せて、溶解槽に送られ、シクロヘキサン(凝固点6.5℃、沸点81.4℃)93%、メチルシクロヘキサン(凝固点-126℃、沸点100℃)7%の混合溶媒100部にフィルム粉砕物17.6部(濃度15%)を添加、吸着剤として酸性白土(水澤化学工業社製、製品名「ミズカエース#20」)を0.53部添加し、70℃で2時間以上攪拌した。
この溶液を、ラヂオライト#300を濾過床として、圧力0.25MPa(出口は大気開放)で加圧濾過(石川島播磨重工社製、製品名「フンダフィルター」)して吸着剤を除去し、無色透明な溶液を得た。次いで前記フィルム粉砕物100部あたり酸化防止剤:ペンタエリスリトールテトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート](チバ・スペシャルティ・ケミカルズ社製、製品名「イルガノックス1010」)を0.5部となるように溶解させた。次いで、ゼータープラスフィルター30H(キュノーフィルター社製、孔径0.5~1μm)にて順次濾過しさらに別の金属ファイバー製フィルター(孔径0.4μm、ニチダイ社製)にて濾過して微小な固形分を除去した。
次いで、上記溶液を、円筒型濃縮乾燥器(日立製作所社製)を用いて、温度270℃、圧力1kPa以下で、溶液から、溶媒であるシクロヘキサン及びその他の揮発成分を除去し、溶融状態のポリマーを270℃でポリマーフィルター(富士フィルター製)を入り口側圧力5.2MPa、出口側圧力2.0MPaで通して、濃縮機に直結したダイから溶融状態でストランド状に押し出すことにより溶融ろ過を行い、冷却後、開環重合体水素添加物のペレットBを再生脂環式構造含有重合体樹脂として得た。
フィルム粉砕物の溶解時間、押出成形後のダイの出口への付着物(目ヤニ)発生の程度、ペレットBの異物発生の程度、およびペレットBのΔYiを評価した。
得られたペレットBを、空気を流通させた熱風乾燥器を用いて70℃で2時間乾燥して水分を除去した後、65mmφのスクリューを備えた樹脂溶融混練機を有するTダイ式フィルム溶融押出し成形機(Tダイ幅500mm)を使用し、クラス10,000以下のクリーンルーム内で、溶融樹脂温度229℃、Tダイ温度229℃の成形条件にて、厚さ100μm、幅500mmの未延伸フィルムBを押出し成形した。得られたシートはロールに巻き取り回収した。
巻き取り回収した上記シートを、ロールごと上記と同一のクリーンルーム内に設置された延伸装置に取り付け、加熱ロールにて139℃(Tg+10℃)に加熱した後、回転速度の異なる第一ロール、第二ロールの順に通過させながら、シートを押出方向に2.0倍の延伸倍率で、延伸速度(引っ張り速度)15mm/秒にて一軸延伸し、延伸フィルムBを再生延伸フィルム(再生成形体)として得た。
得られた延伸フィルムBの外観欠点を評価した。
フィルム粉砕物の混合溶媒への溶解の際に、混合溶媒100部にフィルム粉砕物23.5部(濃度19%)を添加した以外は、実施例1と同様に行った。
混合溶媒として、シクロヘキサン93%、トルエン(凝固点-93℃、沸点111℃)7%の混合溶媒(実施例3)、シクロヘキサン98%、メチルシクロヘキサン2%の混合溶媒(実施例4)、またはシクロヘキサン81%、メチルシクロヘキサン19%の混合溶媒(実施例6)を用いた以外は、実施例1と同様に行った。
原料成形体として、易接着層(ポリウレタン層)を形成していない基材フィルムを用いた以外は、実施例1と同様に行った。
溶融ろ過を行わなかった以外は、実施例1と同様に行った。
吸着剤として活性白土(水澤化学工業社製 製品名「ガレオンアース」、実施例8)または活性アルミナ(住友アルケム株式会社製 製品名「A-11」、実施例9)を用いた以外は、実施例1と同様に行った。
フィルム粉砕物を20mm穴のパンチングプレートを通して回収した以外は、実施例1と同様に行った。
原料成形体の製造において、原料用開環重合体樹脂に代えて下記製造例2で調製した共重合体B(原料付加型脂環式構造含有重合体樹脂)を用いた以外は、実施例1と同様に行った。
<<環状オレフィンと鎖状オレフィンの共重合体(共重合体B)の調製>>
シクロヘキサン258リットルを装入した反応容器に、常温、窒素気流下でノルボルネン(120kg)を加え、5分間撹拌を行った。さらにトリイソブチルアルミニウムを系内の濃度が1.0mL/リットルとなるように添加した。続いて、撹拌しながら常圧でエチレンを流通させ系内をエチレン雰囲気とした。オートクレーブの内温を70℃に保ち、エチレンにて内圧がゲージ圧で6kg/cm2となるように加圧した。10分間撹拌した後、予め用意したイソプロピリデン(シクロペンタジエニル)(インデニル)ジルコニウムジクロリド及びメチルアルモキサンを含むトルエン溶液0.4リットルを系内に添加することによって、エチレンとノルボルネンとの共重合反応を開始させた。このときの触媒濃度は、全系に対してイソプロピリデン(シクロペンタジエニル)(インデニル)ジルコニウムジクロリドが0.018mmol/リットルであり、メチルアルモキサンが8.0mmol/リットルである。この共重合反応中、系内にエチレンを連続的に供給することにより、温度を70℃、内圧をゲージ圧で6kg/cm2に保持した。60分後、イソプロピルアルコールを添加することにより、共重合反応を停止した。脱圧後、ポリマー溶液を取り出し、その後、水1m3に対し濃塩酸5リットルを添加した水溶液と1:1の割合で強撹拌下に接触させ、触媒残渣を水相へ移行させた。この接触混合液を静置したのち、水相を分離除去し、さらに水洗を2回行い、重合液相を精製分離した。
次いで精製分離された重合液相を、3倍量のアセトンと強撹拌下で接触させ、共重合体を析出させた後、固体部(共重合体)を濾過により採取し、アセトンで十分洗浄した。さらに、未反応のモノマーを抽出するため、この固体部を40kg/m3となるようにアセトン中に投入した後、60℃で2時間の条件で抽出操作を行った。抽出処理後、固体部を濾過により採取し、窒素流通下、130℃、350mmHgで12時間乾燥し、エチレン・ノルボルネン共重合体(共重合体B)を得た。
製造例1のA-1-2において開環重合体水素添加物のペレットAを調製したのと同様にして、エチレン・ノルボルネン共重合体(共重合体B)をペレット化した。このペレット化されたエチレン・ノルボルネン共重合体(共重合体B)の重量平均分子量(Mw)は96,000、分子量分布(Mw/Mn)は2.4、Tgは138℃であった。
混合溶媒として、シクロヘキサン99%、メチルシクロヘキサン1%の混合溶媒(比較例1)またはシクロヘキサン78%、メチルシクロヘキサン22%の混合溶媒(比較例2)を用いた以外は、実施例1と同様に行った。
混合溶媒に代えて、シクロヘキサンのみを溶媒として用いた以外は、実施例1と同様に行った。
混合溶媒に代えて、シクロヘキサンのみを溶媒として用いた以外は、実施例11と同様に行った。
A.O 酸化防止剤
ΔYi 黄色度
Claims (11)
- 脂環式構造含有重合体を含む樹脂成形体の再利用方法であって、該樹脂成形体を粉砕して成形体粉砕物を得る工程、および成形体粉砕物を、混合溶媒100重量%に対して80重量%以上98重量%以下のシクロヘキサンと、2重量%以上20重量%以下の凝固点-40℃以下の炭化水素系または芳香族系の溶剤とを含む混合溶媒に溶解して重合体溶液を得る工程を含むことを特徴とする、脂環式構造含有重合体を含む樹脂成形体の再利用方法。
- 樹脂成形体を粉砕する工程と成形体粉砕物を溶解する工程との間に、成形体粉砕物をφ3mm以上15mm以下の篩で篩がけする工程をさらに含むことを特徴とする、請求項1記載の樹脂成形体の再利用方法。
- 溶剤の沸点が、150℃以下である、請求項1または2記載の樹脂成形体の再利用方法。
- 成形体粉砕物溶解系に吸着剤を添加する工程をさらに含むことを特徴とする、請求項1~3の何れか一項に記載の樹脂成形体の再利用方法。
- 吸着剤が、酸性白土、活性白土、活性アルミナ、またはゼオライトである、請求項4記載の樹脂成形体の再利用方法。
- 重合体溶液を溶液状態でろ過して異物、吸着剤を除去する工程をさらに含むことを特徴とする、請求項1~5の何れか一項に記載の樹脂成形体の再利用方法。
- 溶液をろ過するときの重合体溶液中の、混合溶媒と成形体粉砕物との合計量に対する成形体粉砕物の量の割合が、10重量%以上20重量%以下である、請求項6記載の樹脂成形体の再利用方法。
- 重合体溶液から混合溶媒を除去して脂環式構造含有重合体を含む樹脂を回収する工程と、回収した樹脂を溶融する工程と、溶融した樹脂を溶融状態でろ過する工程をさらに含むことを特徴とする、請求項1~7の何れか一項に記載の樹脂成形体の再利用方法。
- 脂環式構造含有重合体のガラス転移温度が、70℃以上170℃以下である、請求項1~8の何れか一項に記載の樹脂成形体の再利用方法。
- 脂環式構造含有重合体が、ノルボルネン系重合体、単環の環状オレフィン系重合体、環状共役ジエン系重合体、ビニル脂環式炭化水素重合体、及びこれらの水素添加物からなる群より選ばれ、かつ脂環式構造含有重合体が、非晶性樹脂である、請求項1~9の何れか一項に記載の樹脂成形体の再利用方法。
- 原料としての樹脂成形体が、100nm以下の厚みのウレタン層を有する、請求項1~10の何れか一項に記載の樹脂成形体の再利用方法。
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JPH11293030A (ja) * | 1998-04-07 | 1999-10-26 | Nippon Zeon Co Ltd | 脂環式構造含有重合体樹脂成形体の再利用方法 |
JP2000063558A (ja) * | 1998-08-25 | 2000-02-29 | Nippon Zeon Co Ltd | 脂環式構造含有重合体を含む成形体の再利用方法 |
JP2002321302A (ja) | 2001-04-26 | 2002-11-05 | Nippon Zeon Co Ltd | 脂環式構造含有重合体樹脂積層体 |
JP2006037049A (ja) * | 2004-07-30 | 2006-02-09 | Nissan Motor Co Ltd | ポリプロピレン製自動車部品のリサイクル方法並びにポリプロピレン製廃材を利用した塗料及びその製造方法 |
JP2006187764A (ja) * | 2004-12-10 | 2006-07-20 | Tokyo Electric Power Co Inc:The | 廃光ファイバーケーブルのマテリアルリサイクル方法 |
JP2008511687A (ja) * | 2004-02-13 | 2008-04-17 | トータル・ペトロケミカルズ・リサーチ・フエリユイ | 汚染防止剤の存在下でのオレフィン重合方法 |
JP2012523970A (ja) * | 2009-04-17 | 2012-10-11 | エレマ エンジニアリング リサイクリング マシネン ウント アンラーゲン ゲゼルシャフト ミット ベシュレンクテル ハフトフング | プラスチック材料のリサイクル方法 |
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JPH11293029A (ja) | 1998-04-07 | 1999-10-26 | Nippon Zeon Co Ltd | 脂環式構造含有重合体樹脂成形体の再利用方法 |
JPH11291247A (ja) | 1998-04-07 | 1999-10-26 | Nippon Zeon Co Ltd | 脂環式構造含有重合体樹脂成形体の再利用方法 |
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- 2022-01-21 WO PCT/JP2022/002283 patent/WO2022163543A1/ja active Application Filing
- 2022-01-21 EP EP22745764.5A patent/EP4286463A1/en active Pending
- 2022-01-21 CN CN202280011236.8A patent/CN116783243A/zh active Pending
- 2022-01-21 US US18/260,248 patent/US20240052127A1/en active Pending
- 2022-01-21 JP JP2022578340A patent/JPWO2022163543A1/ja active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS63179953A (ja) | 1987-01-21 | 1988-07-23 | Asahi Chem Ind Co Ltd | 重合体組成物の製造方法 |
JPH01168643A (ja) | 1987-12-23 | 1989-07-04 | Sumitomo Chem Co Ltd | フェノール系化合物およびこれを有効成分とするブタジエン系ポリマー用安定剤 |
JPH11293030A (ja) * | 1998-04-07 | 1999-10-26 | Nippon Zeon Co Ltd | 脂環式構造含有重合体樹脂成形体の再利用方法 |
JP2000063558A (ja) * | 1998-08-25 | 2000-02-29 | Nippon Zeon Co Ltd | 脂環式構造含有重合体を含む成形体の再利用方法 |
JP2002321302A (ja) | 2001-04-26 | 2002-11-05 | Nippon Zeon Co Ltd | 脂環式構造含有重合体樹脂積層体 |
JP2008511687A (ja) * | 2004-02-13 | 2008-04-17 | トータル・ペトロケミカルズ・リサーチ・フエリユイ | 汚染防止剤の存在下でのオレフィン重合方法 |
JP2006037049A (ja) * | 2004-07-30 | 2006-02-09 | Nissan Motor Co Ltd | ポリプロピレン製自動車部品のリサイクル方法並びにポリプロピレン製廃材を利用した塗料及びその製造方法 |
JP2006187764A (ja) * | 2004-12-10 | 2006-07-20 | Tokyo Electric Power Co Inc:The | 廃光ファイバーケーブルのマテリアルリサイクル方法 |
JP2012523970A (ja) * | 2009-04-17 | 2012-10-11 | エレマ エンジニアリング リサイクリング マシネン ウント アンラーゲン ゲゼルシャフト ミット ベシュレンクテル ハフトフング | プラスチック材料のリサイクル方法 |
Also Published As
Publication number | Publication date |
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EP4286463A1 (en) | 2023-12-06 |
KR20230138945A (ko) | 2023-10-05 |
JPWO2022163543A1 (ja) | 2022-08-04 |
CN116783243A (zh) | 2023-09-19 |
US20240052127A1 (en) | 2024-02-15 |
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